EP0642575A1 - Pumpable alkaline cleaning concentrates. - Google Patents
Pumpable alkaline cleaning concentrates.Info
- Publication number
- EP0642575A1 EP0642575A1 EP93909939A EP93909939A EP0642575A1 EP 0642575 A1 EP0642575 A1 EP 0642575A1 EP 93909939 A EP93909939 A EP 93909939A EP 93909939 A EP93909939 A EP 93909939A EP 0642575 A1 EP0642575 A1 EP 0642575A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- cleaner concentrates
- sodium
- cleaner
- concentrates according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012141 concentrate Substances 0.000 title claims abstract description 70
- 238000004140 cleaning Methods 0.000 title claims abstract description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 24
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 229920000223 polyglycerol Polymers 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 239000000243 solution Substances 0.000 claims description 29
- 239000002736 nonionic surfactant Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- -1 alkali metal salts Chemical class 0.000 claims description 20
- 239000003945 anionic surfactant Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- 235000011187 glycerol Nutrition 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 11
- 150000002191 fatty alcohols Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 11
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 11
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 10
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 235000019351 sodium silicates Nutrition 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000004435 Oxo alcohol Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 25
- 239000012459 cleaning agent Substances 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000000176 sodium gluconate Substances 0.000 description 4
- 235000012207 sodium gluconate Nutrition 0.000 description 4
- 229940005574 sodium gluconate Drugs 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 238000007730 finishing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- ZKPUPHSBFMNFHO-UHFFFAOYSA-N [ClH]1C=CC=C1 Chemical compound [ClH]1C=CC=C1 ZKPUPHSBFMNFHO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
Definitions
- the invention relates to storage-stable, pumpable, alkaline cleaning concentrates, in particular for the industrial cleaning of metallic surfaces based on concentrated aqueous dispersions of alkaline builders, nonionic and / or anionic surfactants and stabilizers in alkali metal hydroxide solutions.
- the aqueous solutions of the alkaline cleaning agents have a pH of approx. 11-14. They are particularly suitable for difficult cleaning tasks, for example for removing thick oil and pigment contaminations in repair shops and for cleaning containers and systems. Furthermore, this type of product is used in particular for the fine cleaning of metallic surfaces, metallic clean surfaces being required. This applies, for example, to cleaning before and after hardening processes strip steel before annealing and coating, as well as pre-treating workpieces in electroplating, phosphating, painting and Erna 11. With these cleaning solutions, a very high level of purity of the workpiece surface is achieved with a good dirt-carrying capacity of the bath.
- Typical alkaline cleaning agents are usually produced as a powder by mixing 80 to 100% by weight of alkaline builder substances and 0 to 20% by weight of various anionic and / or nonionic surfactants.
- the most common inorganic builders are alkaline silicates, phosphates and carbonates of sodium and / or potassium.
- gluconates, alkanolamines, polycarboxylic acids, polyoxycarbonic acids and phosphonates are also used as complexing agents.
- the surfactant mixtures consist of low and highly ethoxylated and propoxylated alkylphenols and / or fatty alcohols with different chain lengths and / or fatty amines with different chain lengths and / or fatty acids or sulfonic acids.
- These ingredients are represented in the alkaline cleaning agents in various combinations and relative concentrations.
- the composition of an optimal product can usually only be found empirically by means of a special sample processing.
- Powdery cleaning agents have a strong tendency to dust and can therefore cause annoyance or even endanger the user when dispensing.
- Nonylphenol ethoxylates, fatty alcohol ethoxylates, fatty acids and alkylbenzenesulfonates are then unsuitable for cleaning agents of this type.
- Ch. Roßmann gives an overview of two-component cleaners which contain sodium hydroxide in a separate solution in "Rational pretreatment by continuous operation of degreasing baths", Metall Chemistry, Vol. 39 (1985), pages 41 to 44.
- the usual industrial industrial cleaners are usually divided into silicate and phosphate cleaners.
- the powdered silicate cleaners based on sodium metasilicate and caustic soda are typically characterized by the SiO 2 / Na 2 O weight or molar ratio that occurs when the products are dissolved in water.
- Such cleaners can be dissolved in water at ambient temperature up to a maximum concentration of approx. 100 g / l if the corresponding sodium salts and caustic soda are used.
- solutions with a maximum concentration of approx. 500 g / 1 result.
- US Pat. No. 4,147,650 also describes an alkaline slurry which is to be used for automatic dishwashing detergents.
- This aqueous slurry contains alkali metal hydroxides and / or silicates as alkaline builders, sodium hypochlorite as a chlorine source and sodium tripolyphosphate or sodium pyrophosphate or other condensed phosphates as well as sodium polyacrylate or sodium polymethacrylate as water conditioning agent.
- US-A-4 521 332 relates to cleaner dispersions for cleaning rolled steel strip prior to its further processing.
- These storage-stable, highly alkaline, aqueous dispersions contain sodium hydroxide, sodium carbonate as adjusting agents, alkali metal phosphates as builders and also chelating agents, nonionic surfactants and polyacrylic acid as dispersants.
- DE-A-37 08 330 also discloses liquid, alkaline cleaner concentrates for cleaning metal surfaces before finishing or processing processes, which have the following components: a) 80 to 99.7% by weight of an aqueous solution of a builder or builder mixture containing 50 to 60% by weight of water and at least one alkali metal silicate and / or phosphate and b) 0.3 to 22% by weight of a surfactant combination consisting of anionic surfactants, nonionic surfactants and alkyl glucosides.
- a surfactant combination consisting of anionic surfactants, nonionic surfactants and alkyl glucosides.
- the object of the present invention was to provide pumpable alkaline cleaner concentrates based on aqueous dispersions of alkaline builder substances, alkali metal hydroxides and nonionic and / or anionic surfactants with high storage stability.
- a destabilization of the dispersion often occurs after a few days, which takes place in a phase separation, i.e. the deposition of solid components.
- Another object of the present invention is to incorporate nonionic and / or anionic surfactants stably in highly concentrated builder dispersions.
- Another object of the present invention is to provide a pumpable cleaner concentrate for cleaning metal surfaces, in particular steel, non-ferrous metal, copper, aluminum and zinc, which are then to be subjected to finishing processes such as phosphating, electroplating, enamelling, painting, etc.
- the cleaner concentrates according to the invention are also intended to be used in the intermediate cleaning before processing processes, for example before the annealing step.
- storage-stable, pumpable, alkaline cleaner concentrates consist of a concentrated aqueous dispersion of a builder or builder mixture as well as nonionic and / or anionic surfactants in alkali metal hydroxide solutions.
- the present invention accordingly relates to storage-stable, pumpable, alkaline cleaner concentrates, consisting of aqueous dispersions based on alkali metal hydroxides, the alkali metal silicates and / or alkali metal phosphates as alkaline builder substances and nonionic and / or anionic surfactants and, if appropriate, further builder substances and / or complexing agents and / or further dispersed active ingredients or auxiliaries, characterized in that they have a combination of a) polyacrylic acid and / or alkali metal polyacrylates and b) glycerol and / or polyglycerol as stabilizers.
- the dispersions provided according to the invention are distinguished by the following properties:
- the cleaner concentrates according to the invention are based on aqueous solutions of alkali metal hydroxides which contain the alkaline builder substances, the nonionic and / or anionic surfactants, the stabilizers and the ingredients, if appropriate, to be added in dispersed form.
- alkali metal hydroxides which contain the alkaline builder substances, the nonionic and / or anionic surfactants, the stabilizers and the ingredients, if appropriate, to be added in dispersed form.
- the cleaner concentrates according to the invention contain such sodium silicates in an amount of 5 to 80% by weight, based on the aqueous sodium hydroxide solution.
- the molar ratio SiO2 / a2O of this combination shifts to lower values.
- the resulting SiO 2 / Na 2 O molar ratio, based on the combination of sodium silicate and sodium hydroxide is preferably in the range from 0.1: 1 to 0.5: 1.
- the cleaner concentrates according to the invention can contain alkali metal phosphates as alkaline builder substances, which are present either together with the alkali metal silicates or instead of them dispersed in the sodium hydroxide solution.
- alkali metal phosphates sodium triphosphate (also called tripolyphosphate) and / or sodium pyrophosphate are preferably used as alkali metal phosphates, sodium pyrophosphate being preferred is.
- the cleaner concentrates according to the invention contain such sodium phosphates in an amount of 5 to 50% by weight, preferably in an amount of 10 to 50% by weight, in each case based on the aqueous sodium hydroxide solution.
- nonionic surfactants to be used in the context of the invention are: ethoxylated or propoxylated alcohols, phenols and amines.
- fatty alcohols with a chain length of 12 to 18 carbon atoms oxo alcohols with a chain length of 9 to 15 carbon atoms
- nonylphenol and fatty amines with a chain length of 12 to 18 carbon atoms each with 1 to 14 mol ethylene oxide (E0 ) or propylene oxide (PO).
- Examples include:
- anionic surfactants to be used in the context of the invention are: straight-chain or branched, saturated or unsaturated carboxylic acids having 10 to 18 carbon atoms and their alkali metal salts, preferably sodium salts, in particular corresponding fatty acid soaps; Alkylbenzenesulfonates with 8 to 18 carbon atoms in the alkyl radical; Alkanesulfonates with 12 to 18 carbon atoms in the alkane radical; ⁇ -olefin sulfonates with 12 to 18 carbon atoms in the olefin radical; ⁇ -sulfo fatty acid esters of C ⁇ 2 b "- s cis fatty acid methyl ester; fatty alcohol sulfates with 8 to 18 carbon atoms in the fatty alcohol residue and Fatty alcohol ether sulfates with 12 to 16 carbon atoms in the fatty alcohol residue and 2 to 4 moles of ethylene oxide.
- the cleaner concentrates according to the invention contain such nonionic and / or anionic surfactants in an amount of 0.1 to 10% by weight, preferably in an amount of 1 to 3% by weight, in each case based on the total composition of the cleaner concentrates.
- the nonionic surfactants can be used for cleaning, emulsifying and defoaming as required.
- nonionic surfactants can also be used to meet various cleaning solution requirements. The same applies to mixtures of anionic surfactants and to mixtures of nonionic and anionic surfactants. In general, the use of nonionic surfactants is preferred.
- the essential constituents of the cleaner concentrates according to the invention also contain a combination of a) polyacrylic acid and / or alkali metal polyacrylates and b) glycerol and / or polyglycerol to stabilize the dispersion.
- the cleaner concentrates polyacrylic acid and / or alkali metal polyacrylates in an amount of 0.5 to 10% by weight, in particular in an amount of 2 to 6% by weight, based in each case on the solid dispersed in the dispersion, contain.
- polyacrylic acid proves to be more advantageous than the neutralized sodium form with the same molecular mass in terms of the dispersion stability achieved.
- the polyacrylic acids to be used are already known from US Pat. No. 4,521,332.
- polyacrylic acids is preferred over the salts because, in contrast to the salts, the free acids are significantly more soluble in water and are therefore very good in a first production step, also in combination with the nonionic and / or anionic surfactants used the solids to be dispersed can be applied.
- the particularly preferred molecular weight of the polyacrylic acids is in the range from 500 to 12,000, preferably below 10,000; best results were obtained using a 63% by weight solution of a polyacrylic acid with a molecular weight of 2,100. Higher molecular weights of the polyacrylic acids only led to increased viscosities with the same active substance contents.
- alkali metal salts of polyacrylic acid such as, for example, sodium polyacrylates, the molecular weight of the sodium must be taken into account in relation to the amount used.
- Glycerol and / or polyglycerol are also part of the stabilizer combination according to the invention. These are present in the cleaner concentrates according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 3% by weight, in each case based on the total composition of the cleaner concentrates.
- polyglycerols are known, for example, from Ullmanns Encyklopadie der industrial chemistry, 4th edition 1976, volume 12, page 374.
- the polyglycerols have relative molecular weights of 166 (6 carbon atoms) to 2238 (90 carbon atoms) and 4 to 32 hydroxyl groups.
- the cleaner concentrates according to the invention can also contain further constituents which are usually used in alkaline cleaning agents.
- additional alkaline builders such as additional alkaline builders, complexing agents, defoamers and corrosion inhibitors.
- compounds which are particularly suitable in the context of the invention are:
- Additional alkaline builder substances alkanolamines, such as mono-, di- or triethanolamine, alkali metal carbonates, such as sodium carbonate, alkali metal gluconates, in particular sodium or potassium gluconate, and further alkali metal hydroxides, i.e. in particular sodium hydroxide.
- alkanolamines such as mono-, di- or triethanolamine
- alkali metal carbonates such as sodium carbonate
- alkali metal gluconates such as sodium or potassium gluconate
- further alkali metal hydroxides i.e. in particular sodium hydroxide.
- the cleaner concentrates according to the invention contain these additional alkaline builder substances in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, in each case based on the total composition of the cleaner concentrates.
- Complexing agents polycarboxylic acids, phosphonic acids, such as hydroxyethane-l, l-diphosphonic acid (HEDP), amino-tris (methylenephosphonic acid) (ATMP), aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), polyoxycarboxylic acids, e.g. Citric acid, and the water-soluble salts of such acids, preferably the sodium salts.
- the cleaning concentrates according to the invention can contain such complexing agents in an amount of 0.5 to 5% by weight, preferably 2 to 4% by weight, in each case based on the total composition of the cleaning concentrates.
- Defoamer C ⁇ / ig fatty alcohol coconut alcohol J polyethylene glycol butyl ether, ethylenediamine + 30E0 + 60P0; in each case in amounts of 0.1 to 5% by weight, based on the total composition of the cleaner concentrates.
- Corrosion inhibitors (for non-ferrous metals) benzotriazole, tolyltriazole; in each case in amounts of 0.1 to 5% by weight, based on the total composition of the cleaner concentrates.
- the procedure is generally as follows:
- the builder substances are firstly treated as solids with the wetting agents used in the cleaner, i.e. the nonionic and / or anionic surfactants, and the stabilizers, i.e. mixed with polyacrylic acid and glycerin / polyglycerin, as well as any other ingredients to be used.
- this mixture is dispersed in technical 40 to 50% by weight aqueous sodium hydroxide solution. It is of course also possible to individually disperse the builders, surfactants, stabilizers and any other ingredients to be used in any order in the aqueous sodium hydroxide solution.
- ROTOR-STATOR systems can be designed as chamber, hole or cone tools. .
- the cleaning concentrates according to the invention can be produced at room temperature. However, it is preferred that this dispersion takes place at elevated temperature, ie at temperatures up to 220 ° C; a temperature range of 50 to 60 ° C. is particularly preferred here. Of course, the cleaning concentrates can be produced both discontinuously and continuously.
- the present invention furthermore relates to the use of the cleaner concentrates according to the invention in the cleaning of metal surfaces, in particular steel, non-ferrous metals, copper, aluminum and zinc before finishing processes such as phosphating, electroplating, enamelling and painting and in intermediate cleaning before processing processes, in particular before Glow.
- cleaner concentrates according to the invention can of course also be used in undiluted form, it is preferred for the purposes of the present invention to use the cleaner concentrates in such a way that an aqueous solution containing 1 to 20% by weight cleaner concentrate is used for the above-mentioned cleaning agents processes. Accordingly, cleaning solutions preferably used contain 10 to 200 g / 1 of the cleaner concentrates according to the invention. For the preparation of dilute application solutions, i.e. Cleaning solutions, the cleaning concentrates are usually dosed directly into the cleaning bath with stirring.
- the advantage of the pumpable, alkaline cleaner concentrates according to the invention is, on the one hand, that they have a high active substance content of builder substances and, at the same time, an extraordinary storage stability and, on the other hand, that they allow simple dosing.
- Suitable products can therefore be offered for all applications in industrial technical cleaning, for example for spraying, brushing, immersion and ultrasonic processes as well as for electrolytic cleaning.
- predetermined cloud points can be set and high-temperature or low-temperature cleaners can be prepared.
- the nonionic surfactants were melted together with the polyacrylic acid solution and the glycerol, and this mixture was then mixed with the builder substances in a laboratory mixer. especially sodium metasilicate and / or sodium pyrophosphate, mixed. This mixture was then stirred into a commercially available 50% by weight sodium hydroxide solution, heated to 60 ° C. and then dispersed using a high-performance disperser.
- the dispersions according to the invention are stable to settling for several weeks at room temperature and show no change in the flow behavior, whereas with dispersions not according to the invention a phase separation could be observed after a relatively short time, making the corresponding products unsuitable for industrial use.
- a pumpable alkaline cleaner concentrate was produced from 53% by weight of a 50% sodium hydroxide solution, 40.3% by weight sodium metasilicate K0 with a particle size distribution of 20% ⁇ 0.4 mm, 40% ⁇ 0 , 2 mm, 20% ⁇ 0.1 mm and 15% ⁇ 0.05 mm (sodium metasilicate K0 - Na2Si ⁇ 3, anhydrous).
- the cleaner concentrate also contained 1.7% by weight of polyacrylic acid (Good-Rite K 752 (63%)) with a molecular weight of 2100 and a sodium content of 0.8% with a pH in the range from 2.2 to 3.
- Suitable nonionic surfactant-based a combination of equal parts of a served C ⁇ -iß fatty alcohols mi 't 14 E0 (0HZ 68 ⁇ 1S 74, AS 100%) and a modified fatty alcohol polyglycol ether based on coconut chlorol with 9.5 EO, butyl ether.
- the mixture of the two surfactants is contained in the cleaning concentrate in an amount of 2% by weight.
- the cleaning concentrate also contains 3% by weight of glycerin.
- Example 2 Analogously to Example 2, but using 0.6% by weight of polyacrylic acid, 9.7% by weight of sodium pyrophosphate and 75.1% by weight of 50% sodium hydroxide solution instead of the formulation constituents correspondingly mentioned in Example 2, it was also possible to use for 8 weeks stable cleaner concentrate can be obtained.
- Comparative Example 1 Using 54.7% by weight of 50% sodium hydroxide solution, 41.5% by weight of the above-mentioned sodium metasilicate, 1.8% by weight of the above-mentioned polyacrylic acid, 2.0% by weight of the above A cleaner concentrate was prepared based on the surfactant, but without the use of glycerol. A phase separation occurred after only 2 days.
- a cleaner concentrate was prepared using 53.9% by weight of the 50% sodium hydroxide solution, 41.0% by weight of the above sodium metasilicate, 2% by weight of the above surfactant base and 3.1% by weight of glycerin. in which, however, a phase separation already occurred after one day.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A composition and process for producing a storable, pumpable alkaline cleaning concentrate comprising an aqueous alkali metal hydroxide having dispersed therein alkaline builder and surfactants, and a stabilizer therefor comprising the combination of: (a) polyacrylic acid or alkali metal polyacrylate; and (b) glycerol or polyglycerol.
Description
Pumpfähioe alkalische ReiniqerkonzentratePumpable alkaline cleaner concentrates
Die Erfindung betrifft lagerstabile, pumpfähige, alkalische Reini¬ gerkonzentrate, insbesondere für die industrielle Reinigung von metallischen Oberflächen auf Basis konzentrierter wäßriger Disper¬ sionen von alkalischen Builderstoffen, nichtionischen und/oder an¬ ionischen Tensiden und Stabilisatoren in Alkali etallhydroxid-Lö- sungen.The invention relates to storage-stable, pumpable, alkaline cleaning concentrates, in particular for the industrial cleaning of metallic surfaces based on concentrated aqueous dispersions of alkaline builders, nonionic and / or anionic surfactants and stabilizers in alkali metal hydroxide solutions.
Die aus reinigungstechnischer Sicht wichtigsten Komponenten dieser Konzentrate sind Builder- und Tensidsysteme. Die Eigenschaften dieser Basismischungen aus Builderstoffen und nichtionischen und/oder anionischen Tensiden werden für den praktischen Einsatz häufig noch durch den Zusatz von weiteren Inhaltsstoffen, wie Kom¬ plexbildnern und Korrosionsinhibitoren, dem jeweils vorliegenden Anwendungsfall angepaßt.From a cleaning point of view, the most important components of these concentrates are builder and surfactant systems. The properties of these base mixtures of builder substances and nonionic and / or anionic surfactants are often adapted for practical use by adding further ingredients, such as complexing agents and corrosion inhibitors, to the particular application at hand.
Die wäßrigen Lösungen der alkalischen Reinigungsmittel besitzen einen pH-Wert von ca. 11-14. Sie sind besonders für schwierige Reinigungsaufgaben, z.B. zur Entfernung von dicken Öl- und Pig¬ mentverschmutzungen in Reparaturbetrieben und zur Behälter- und Anlagenreinigung, geeignet. Weiterhin wird dieser Produkttyp ins¬ besondere zur Feinreinigung von metallischen Oberflächen einge¬ setzt, wobei metallisch reine Oberflächen gefordert sind. Dies gilt beispielsweise bei der Reinigung vor und nach Härteprozessen, bei
der Reinigung von Bandstahl vor der Glühe und vor dem Beschichten sowie bei der Vorbehandlung von Werkstücken in Galvaniken, Phos- phatierungen, Lackierereien und Erna 11 erbetrieben. Mit diesen Reinigungslösungen wird eine sehr hohe Reinheit der Werkstückober¬ fläche bei einem gleichzeitig guten Schmutztragevermögen des Bades erreicht.The aqueous solutions of the alkaline cleaning agents have a pH of approx. 11-14. They are particularly suitable for difficult cleaning tasks, for example for removing thick oil and pigment contaminations in repair shops and for cleaning containers and systems. Furthermore, this type of product is used in particular for the fine cleaning of metallic surfaces, metallic clean surfaces being required. This applies, for example, to cleaning before and after hardening processes strip steel before annealing and coating, as well as pre-treating workpieces in electroplating, phosphating, painting and Erna 11. With these cleaning solutions, a very high level of purity of the workpiece surface is achieved with a good dirt-carrying capacity of the bath.
Typische alkalische Reinigungsmittel werden meist als Pulver durch Mischen von 80 bis 100 Gew.-% alkalischen Builderstoffen und 0 bis 20 Gew.-% verschiedenen anionischen und/oder nichtionischen Ten¬ siden hergestellt. Die gebräuchlichsten anorganischen Builderstoffe sind alkalisch reagierende Silicate, Phosphate und Carbonate von Natrium und/oder Kalium. Je nach Bedarf kommen noch als Komplex¬ bildner Gluconate, Alkanolamine, Polycarbonsäuren, Polyoxycarbon- säuren und Phosphonate zum Einsatz. Die Tensidmischungen bestehen aus niedrig und hoch ethoxylierten und propoxylierten Alkylphenolen und/oder Fettalkoholen mit verschiedener Kettenlänge und/oder Fettaminen mit verschiedenen Kettenlängen und/oder Fettsäuren bzw. Sulfonsäuren. Diese Inhaltsstoffe sind in den alkalischen Reini¬ gungsmitteln in verschiedenen Kombinationen und ReTativkonzentra- tionen vertreten. Die Zusammensetzung eines optimalen Produktes kann in der Regel nur empirisch durch eine spezielle Musterbear¬ beitung gefunden werden.Typical alkaline cleaning agents are usually produced as a powder by mixing 80 to 100% by weight of alkaline builder substances and 0 to 20% by weight of various anionic and / or nonionic surfactants. The most common inorganic builders are alkaline silicates, phosphates and carbonates of sodium and / or potassium. Depending on requirements, gluconates, alkanolamines, polycarboxylic acids, polyoxycarbonic acids and phosphonates are also used as complexing agents. The surfactant mixtures consist of low and highly ethoxylated and propoxylated alkylphenols and / or fatty alcohols with different chain lengths and / or fatty amines with different chain lengths and / or fatty acids or sulfonic acids. These ingredients are represented in the alkaline cleaning agents in various combinations and relative concentrations. The composition of an optimal product can usually only be found empirically by means of a special sample processing.
Pulverförmige Reinigungsmittel neigen stark zum Stauben und können daher beim Dosieren eine Belästigung oder sogar Gefährdung des An¬ wenders verursachen.Powdery cleaning agents have a strong tendency to dust and can therefore cause annoyance or even endanger the user when dispensing.
Derartige Schwierigkeiten können mit flüssigen oder zumindest pumpfähigen Reinigungsprodukten weitgehend vermieden werden, die in der Regel sehr viel einfacher dosiert werden können. Bei der For¬ mulierung derartiger Reinigungsmittel tauchen jedoch zwei Probleme
auf: Natriumverbindungen der Builderstoffe können in der Mehrzahl der Fälle nur bis zu einer maximalen Konzentration von ca. 100 bis 150 g/1 als thermodynamisch stabile Lösungen bei Umgebungstempera¬ tur (Raumtemperatur) konfektioniert werden. Beim Einsatz der ent¬ sprechenden Kaliumverbindungen können dagegen Mengen von ca. 500 g/1 gelöst werden. Die Rohstoffkosten steigen dann allerdings be¬ trächtlich an. Weiterhin ist die Löslichkeit der bewährten Tenside in derartig hoch salzhaltigen, stark alkalischen Lösungen in der Regel völlig ungenügend. Übliche nichtionische Tenside sind über¬ haupt nicht aufzulösen, und bei anionischen Tensiden besteht nur die Möglichkeit, Verbindungen aufzulösen, die eine sehr kurze, we¬ nig hydrophobe C-Kette in der Größenordnung von sechs oder weniger C-Atomen aufweisen. Nonylphenolethoxylate, Fettalkoholethoxylate, Fettsäuren und Alkylbenzolsulfonate sind dann für derartige Reini¬ gungsmittel ungeeignet.Such difficulties can largely be avoided with liquid or at least pumpable cleaning products, which can generally be dosed much more easily. However, two problems arise when formulating such cleaning agents In most cases, sodium compounds of the builder substances can only be assembled as thermodynamically stable solutions at ambient temperature (room temperature) up to a maximum concentration of approximately 100 to 150 g / l. In contrast, when the corresponding potassium compounds are used, amounts of approximately 500 g / l can be dissolved. However, the raw material costs then rise considerably. Furthermore, the solubility of the proven surfactants in such highly saline, strongly alkaline solutions is generally completely inadequate. Usual nonionic surfactants cannot be dissolved at all, and with anionic surfactants there is only the possibility of dissolving compounds which have a very short, slightly hydrophobic C chain of the order of six or fewer C atoms. Nonylphenol ethoxylates, fatty alcohol ethoxylates, fatty acids and alkylbenzenesulfonates are then unsuitable for cleaning agents of this type.
Einen Überblick über Zweikomponentenreiniger, die Natriumhydroxid in einer separaten Lösung enthalten, gibt Ch. Roßmann in "Ratio¬ nelle Vorbehandlung durch kontinuierlichen Betrieb von Entfet¬ tungsbädern", Metalloberfläche, Vol. 39 (1985), Seiten 41 bis 44.Ch. Roßmann gives an overview of two-component cleaners which contain sodium hydroxide in a separate solution in "Rational pretreatment by continuous operation of degreasing baths", Metallfläche, Vol. 39 (1985), pages 41 to 44.
Die gebräuchlichen technischen Industriereiniger werden üblicher¬ weise in Silicat- und Phosphatreiniger unterteilt. Hierbei charak¬ terisiert man die pulverförmigen Silicatreiniger auf Basis von Natriummetasilicat und Ätznatron in der Regel durch das Siθ2/Na2θ- Gewichts- bzw. Molverhältnis, das sich beim Auflösen der Produkte in Wasser einstellt. Derartige Reiniger können bei Umgebungstempe¬ ratur bis zu einer maximalen Konzentration von ca. 100 g/1 in Was¬ ser aufgelöst werden, sofern die entsprechenden Natriumsalze und Ätznatron eingesetzt werden. Finden hingegen die entsprechenden Kaliumsalze und Kaliumhydroxid Verwendung, so resultieren Lösungen mit einer maximalen Konzentration von ca. 500 g/1.
In Chemical Abstracts Vol. 100 (1984), Seite 114, 100:70377k, Re¬ ferat zu JP-A-83/108300, wird ein Geschirrspülmittel auf Basis ei¬ nes alkalischen Slurrys beschrieben, welches 5 bis 10 % NaOHt 15 bis 40 % KOH, 10 bis 35 % Natriumtripolyphosphat, 5 bis 15 % Si i- cate, 0,5 bis 10 % Isoamylen-Maleinsäureanhydrid-Copolymer, 0,5 bis 5 % Polyacrylsäure und 40 bis 60 % Wasser enthält.The usual industrial industrial cleaners are usually divided into silicate and phosphate cleaners. In this case, the powdered silicate cleaners based on sodium metasilicate and caustic soda are typically characterized by the SiO 2 / Na 2 O weight or molar ratio that occurs when the products are dissolved in water. Such cleaners can be dissolved in water at ambient temperature up to a maximum concentration of approx. 100 g / l if the corresponding sodium salts and caustic soda are used. However, if the corresponding potassium salts and potassium hydroxide are used, solutions with a maximum concentration of approx. 500 g / 1 result. Chemical Abstracts Vol. 100 (1984), page 114, 100: 70377k, reference to JP-A-83/108300, describes a dishwashing detergent based on an alkaline slurry which contains 5 to 10% NaOH t 15 to Contains 40% KOH, 10 to 35% sodium tripolyphosphate, 5 to 15% silicates, 0.5 to 10% isoamylene-maleic anhydride copolymer, 0.5 to 5% polyacrylic acid and 40 to 60% water.
Auch die US-A-4 147 650 beschreibt einen alkalischen Slurry, der für maschinelle Geschirrspülmittel Verwendung finden soll. Dieser wäßrige Slurry enthält Alkalimetallhydroxide und/oder -silicate als alkalische Builderstoffe, Natriumhypochlorit als Chlor-Quelle und Natriumtripolyphosphat oder Natriumpyrophosphat oder andere kon¬ densierte Phosphate sowie Natriu polyacrylat oder Natriumpolymeth- acrylat als Wasserkonditionierungsmittel.US Pat. No. 4,147,650 also describes an alkaline slurry which is to be used for automatic dishwashing detergents. This aqueous slurry contains alkali metal hydroxides and / or silicates as alkaline builders, sodium hypochlorite as a chlorine source and sodium tripolyphosphate or sodium pyrophosphate or other condensed phosphates as well as sodium polyacrylate or sodium polymethacrylate as water conditioning agent.
Gegenstand der US-A-4 521 332 sind Reiniger-Dispersionen zur Rei¬ nigung von gewalztem Stahlband vor dessen Weiterverarbeitung. Diese lagerstabilen, hoch-alkalischen, wäßrigen Dispersionen enthalten Natriumhydroxid, Natriumcarbonat als Stellmittel, Alkalimetall- phosphate als Builder sowie ferner Chelatbildner, nichtionische Tenside und Polyacrylsäure als Dispergiermittel.US-A-4 521 332 relates to cleaner dispersions for cleaning rolled steel strip prior to its further processing. These storage-stable, highly alkaline, aqueous dispersions contain sodium hydroxide, sodium carbonate as adjusting agents, alkali metal phosphates as builders and also chelating agents, nonionic surfactants and polyacrylic acid as dispersants.
Aus der DE-A-37 08 330 sind ferner flüssige, alkalische Reiniger¬ konzentrate zur Reinigung von Metalloberflächen vor Veredelungs¬ oder Verarbeitungsprozessen bekannt, die die folgenden Komponenten aufweisen: a) 80 bis 99,7 Gew.-% einer wäßrigen Lösung eines Builders oder Buildergemisches, enthaltend 50 bis 60 Gew.-% Wasser sowie mindestens ein Alkalimetallsilicat und/oder -phosphat und b) 0,3 bis 22 Gew.-% einer Tensidkombination, bestehend aus aπioni- schen Tensiden, nichtionischen Tensiden und Alkylglucosiden. Hier¬ bei handelt es sich jedoch um Lösungen - und nicht um Dispersionen
-, die zudem nur bei Verwendung der speziellen Tensidkombination erhältlich sind.DE-A-37 08 330 also discloses liquid, alkaline cleaner concentrates for cleaning metal surfaces before finishing or processing processes, which have the following components: a) 80 to 99.7% by weight of an aqueous solution of a builder or builder mixture containing 50 to 60% by weight of water and at least one alkali metal silicate and / or phosphate and b) 0.3 to 22% by weight of a surfactant combination consisting of anionic surfactants, nonionic surfactants and alkyl glucosides. However, these are solutions - and not dispersions - which are also only available when using the special surfactant combination.
Dem genannten Stand der Technik gegenüber bestand die Aufgabe der vorliegenden Erfindung in der Bereitstellung pumpfähiger alkali¬ scher Reinigerkonzentrate auf Basis von wäßrigen Dispersionen al¬ kalischer Builderstoffe, Alkalimetallhydroxide und nichtionischer und/oder anionischer Tenside mit hoher Lagerstabilität. Bei im Stand der Technik bekannten Reinigerkonzentraten tritt häufig be¬ reits nach wenigen Tagen eine Destabilisierung der Dispersion auf, die sich in einer Phasentrennung, d.h. dem Absetzen von festen Be¬ standteilen, äußert.In relation to the prior art mentioned, the object of the present invention was to provide pumpable alkaline cleaner concentrates based on aqueous dispersions of alkaline builder substances, alkali metal hydroxides and nonionic and / or anionic surfactants with high storage stability. In the case of cleaner concentrates known in the prior art, a destabilization of the dispersion often occurs after a few days, which takes place in a phase separation, i.e. the deposition of solid components.
Eine weitere Aufgabe der vorliegenden Erfindung besteht darin, nichtionische und/oder anionische Tenside stabil in hochkonzen¬ trierte Builder-Dispersionen einzubringen.Another object of the present invention is to incorporate nonionic and / or anionic surfactants stably in highly concentrated builder dispersions.
Weiterhin besteht die Aufgabe der vorliegenden Erfindung darin, ein pumpfähiges Reinigerkonzentrat zum Reinigen von Metalloberflächen, insbesondere von Stahl, Buntmetall, Kupfer, Aluminium und Zink, die anschließend Veredelungsprozessen wie Phosphatieren, Galvanisieren, Emaillieren, Lackieren etc. unterworfen werden sollen, zur" Verfü¬ gung zu stellen. Auch sollen die erfindungsgemäßen Reinigerkonzen¬ trate Anwendung bei der Zwischenreinigung vor Verarbeitungspro¬ zessen, beispielsweise vor der Glühe, finden.Another object of the present invention is to provide a pumpable cleaner concentrate for cleaning metal surfaces, in particular steel, non-ferrous metal, copper, aluminum and zinc, which are then to be subjected to finishing processes such as phosphating, electroplating, enamelling, painting, etc. The cleaner concentrates according to the invention are also intended to be used in the intermediate cleaning before processing processes, for example before the annealing step.
Die vorstehend genannten Aufgaben werden gelöst durch lagerstabile, pumpfähige, alkalische Reinigerkonzentrate, die aus einer konzen¬ trierten wäßrigen Dispersion eines Builderstoffes oder Builderge- misches sowie nichtionischen und/oder anionischen Tensiden in Alkalimetallhydroxid-Lösungen bestehen.
Gegenstand der vorliegenden Erfindung sind dementsprechend lager¬ stabile, pumpfähige, alkalische Reinigerkonzentrate, bestehend aus wäßrigen Dispersionen auf Basis von Alkalimetallhydroxiden, die Alkalimetallsilicate und/oder Alkalimetallphosphate als alkalische Builderstoffe sowie nichtionische und/oder anionische Tenside und gegebenenfa ls weitere Bu derstoffe und/oder Komplexbildner und/oder weitere an sich bekannte Wirk- oder Hilfsstoffe dispergiert enthalten, dadurch gekennzeichnet, daß sie als Stabi¬ lisatoren eine Kombination aus a) Polyacrylsäure und/oder Alkali etallpolyacrylaten und b) Glycerin und/oder Polyglycerin aufweisen.The above-mentioned objects are achieved by storage-stable, pumpable, alkaline cleaner concentrates, which consist of a concentrated aqueous dispersion of a builder or builder mixture as well as nonionic and / or anionic surfactants in alkali metal hydroxide solutions. The present invention accordingly relates to storage-stable, pumpable, alkaline cleaner concentrates, consisting of aqueous dispersions based on alkali metal hydroxides, the alkali metal silicates and / or alkali metal phosphates as alkaline builder substances and nonionic and / or anionic surfactants and, if appropriate, further builder substances and / or complexing agents and / or further dispersed active ingredients or auxiliaries, characterized in that they have a combination of a) polyacrylic acid and / or alkali metal polyacrylates and b) glycerol and / or polyglycerol as stabilizers.
Die erfindungsgemäß bereitgestellten Dispersionen zeichnen sich durch folgende Eigenschaften aus:The dispersions provided according to the invention are distinguished by the following properties:
sehr hohe Feststoff-Aktivsubstanz-Gehalte; sehr geringe Mengen zusätzlich benötigter Dispersionshilfsmit¬ tel, die alkalistabil, preiswert und zudem zum großen Teil (schnell) biologisch abbaubar sind; die üblicherweise in der Reinigung verwendeten Netzmittel sind in der Dispersion chemisch stabil und separieren nicht; die Dispersionen haben - verglichen mit den Pulverprodukten - eine verbesserte Lösegeschwindigkeit.very high solid active substance contents; very small amounts of additional dispersion auxiliaries required, which are alkali-stable, inexpensive and moreover (largely) biodegradable; the wetting agents usually used in cleaning are chemically stable in the dispersion and do not separate; the dispersions have an improved dissolution rate compared to the powder products.
Als Alkalimetalle finden im Sinne der Erfindung vorzugsweise Na¬ trium und/oder Kalium Verwendung. Hierbei werden auch Mischungen entsprechender Natrium- und Kaliumverbindungen eingesetzt. Insbe¬ sondere bevorzugt ist jedoch die Verwendung von Natrium als Alka- limetall.
Wie vorstehend bereits gesagt, basieren die erfindungsgemäßen Rei¬ nigerkonzentrate auf wäßrigen Lösungen von Alkalimetallhydroxiden, welche die alkalischen Builderstoffe, die nichtionischen und/oder anionischen Tenside, die Stabilisatoren sowie die gegebenenfalls zuzusetzenden Inhaltsstoffe in dispergierter Form enthalten. Im Sinne der vorliegenden Erfindung ist es bevorzugt, als wäßrige Alkalimetallhydroxid-Lösung eine 40 bis 50 Gew.-%ige wäßrige Lösung von Natriumhydroxid einzusetzen.For the purposes of the invention, sodium and / or potassium are preferably used as alkali metals. Mixtures of appropriate sodium and potassium compounds are also used. However, the use of sodium as alkali metal is particularly preferred. As already mentioned above, the cleaner concentrates according to the invention are based on aqueous solutions of alkali metal hydroxides which contain the alkaline builder substances, the nonionic and / or anionic surfactants, the stabilizers and the ingredients, if appropriate, to be added in dispersed form. For the purposes of the present invention, it is preferred to use a 40 to 50% by weight aqueous solution of sodium hydroxide as the aqueous alkali metal hydroxide solution.
Als alkalische Builderstoffe werden erfindungsgemäß Alkalimetall¬ silicate und/oder Alkalimetallphosphate eingesetzt, wobei die ent¬ sprechenden Natriumverbindungen bevorzugt sind. Wenn hier von Alkalimetallsilicaten die Rede ist, so werden erfindungsgemäß be¬ vorzugt Natriumsilicate mit einem MolVerhältnis Siθ2/ a2θ im Be¬ reich von 1:1 bis 3,5:1 eingesetzt, wobei Natriumsilicate mit einem MolVerhältnis Siθ2/ a2θ = 1:1 insbesondere bevorzugt sind. Die erfindungsgemäßen Reinigerkonzentrate enthalten derartige Natrium¬ silicate in einer Menge von 5 bis 80 Gew.-%, bezogen auf die wä߬ rige Natriumhydroxid-Lösung. Aufgrund der Kombination von Natrium- silicaten mit Natriumhydroxid verschiebt sich nun das Molverhältnis Siθ2/ a2θ dieser Kombination zu geringeren Werten. Erfindungsgemäß ist es bevorzugt, daß das resultierende Molverhältnis Siθ2/Na2θ - bezogen auf die Kombination von Natriumsilicat und Natriumhydroxid - vorzugsweise im Bereich von 0,1:1 bis 0,5:1 liegt.According to the invention, alkali metal silicates and / or alkali metal phosphates are used as alkaline builder substances, the corresponding sodium compounds being preferred. If alkali metal silicates are mentioned here, sodium silicates with a molar ratio SiO 2 / a 2 O in the range from 1: 1 to 3.5: 1 are preferably used according to the invention, sodium silicates with a mol ratio SiO 2 / a2 O = 1: 1 in particular are preferred. The cleaner concentrates according to the invention contain such sodium silicates in an amount of 5 to 80% by weight, based on the aqueous sodium hydroxide solution. Due to the combination of sodium silicates with sodium hydroxide, the molar ratio SiO2 / a2O of this combination shifts to lower values. According to the invention, it is preferred that the resulting SiO 2 / Na 2 O molar ratio, based on the combination of sodium silicate and sodium hydroxide, is preferably in the range from 0.1: 1 to 0.5: 1.
Wie bereits gesagt, können die erfindungsgemäßen Reinigerkonzen¬ trate als alkalische Builderstoffe Alkalimetallphosphate enthalten, die entweder zusammen mit den Alkalimetallsilicaten oder anstelle derselben dispergiert in der Natriumhydroxid-Lösung vorliegen. Er¬ findungsgemäß werden als Alkalimetallphosphate vorzugsweise Natriu triphosphat (auch Tripolyphosphat genannt) und/oder Natriu pyrophosphat eingesetzt, wobei Natriumpyrophosphat bevorzugt
ist. Die erfindungsgemäßen Reinigerkonzentrate enthalten derartige Natriumphosphate in einer Menge von 5 bis 50 Gew.-%, vorzugsweise in einer Menge von 10 bis 50 Gew.-%, jeweils bezogen auf die wä߬ rige Natriumhydroxid-Lösung.As already mentioned, the cleaner concentrates according to the invention can contain alkali metal phosphates as alkaline builder substances, which are present either together with the alkali metal silicates or instead of them dispersed in the sodium hydroxide solution. According to the invention, sodium triphosphate (also called tripolyphosphate) and / or sodium pyrophosphate are preferably used as alkali metal phosphates, sodium pyrophosphate being preferred is. The cleaner concentrates according to the invention contain such sodium phosphates in an amount of 5 to 50% by weight, preferably in an amount of 10 to 50% by weight, in each case based on the aqueous sodium hydroxide solution.
Als Beispiele für die im Sinne der Erfindung einzusetzenden, nichtionischen Tenside seien genannt: Ethoxylierte bzw. propoxylierte Alkohole, Phenole und Amine. Insbesondere verwendet werden Fettalkohole mit einer Kettenlänge von 12 bis 18 C-Atomen, Oxoalkohole mit einer Kettenlänge von 9 bis 15 C-Atomen, Nonylphenol sowie Fettamine mit einer Kettenlänge von 12 bis 18 C-Atomen, jeweils mit 1 bis 14 Mol Ethylenoxid (E0) bzw. Propylen- oxid (PO).Examples of nonionic surfactants to be used in the context of the invention are: ethoxylated or propoxylated alcohols, phenols and amines. In particular, fatty alcohols with a chain length of 12 to 18 carbon atoms, oxo alcohols with a chain length of 9 to 15 carbon atoms, nonylphenol and fatty amines with a chain length of 12 to 18 carbon atoms, each with 1 to 14 mol ethylene oxide (E0 ) or propylene oxide (PO).
Beispielhaft seien hier genannt:Examples include:
Cl2-18"Fetta"l-°h0'le' ethoxyliert mit 4, 9 oder 14 Mol E0; Oleyl- alkohol, ethoxyliert mit 2 oder 10 Mol EO; Cg_i2-0xoalkohol, eth¬ oxyliert mit 6 EO; Cιχ_i5-0xoalkohole, ethoxyliert mir 7 oder 9 Mol EO; Nonylphenol, ethoxyliert mit 6 oder 12 Mol EO; Ci^is-Fet amine (Kokosamin), ethoxyliert mit 12 Mol EO; Ciμiβ-Fettamine (Talg- amin), ethoxyliert mit 12 Mol EO. Auch die entsprechenden prop- oxylierten Verbindungen können Verwendung finden.Cl2-18 "F etta" l- ° h 0 ' l e ' ethoxylated with 4, 9 or 14 mol E0; Oleyl alcohol, ethoxylated with 2 or 10 mol EO; Cg_i2-0xoalkohol, eth¬ oxylated with 6 EO; Cιχ_i5-0xoalkohole, ethoxylates me 7 or 9 mol EO; Nonylphenol, ethoxylated with 6 or 12 moles of EO; Ci ^ is-Fet amine (coconut amine), ethoxylated with 12 mol EO; Ciμiβ-fatty amines (tallow amine), ethoxylated with 12 mol EO. The corresponding propoxylated compounds can also be used.
Als Beispiele für die im Sinne der Erfindung einzusetzenden anio¬ nischen Tenside seien genannt: Geradkettige oder verzweigte, ge¬ sättigte oder ungesättigte Carbonsäuren mit 10 bis 18 C-Atomen und deren Alkalimetallsalze, vorzugsweise Natriumsalze, insbesondere entsprechende Fettsäureseifen; Alkylbenzolsulfonate mit 8 bis 18 C-Atomen im Alkylrest; Alkansulfonate mit 12 bis 18 C-Atomen im Alkanrest; α-Olefinsulfonate mit 12 bis 18 C-Atomen im Olefinrest; α-Sulfofettsäureester von Cχ2 b"-s Cis-Fettsäuremethylester; Fett¬ alkoholsulfate mit 8 bis 18 C-Atomen im Fettalkoholrest sowie
Fettalkoholethersulfate mit 12 bis 16 C-Atomen im Fettalkoholrest und 2 bis 4 Mol Ethylenoxid.Examples of the anionic surfactants to be used in the context of the invention are: straight-chain or branched, saturated or unsaturated carboxylic acids having 10 to 18 carbon atoms and their alkali metal salts, preferably sodium salts, in particular corresponding fatty acid soaps; Alkylbenzenesulfonates with 8 to 18 carbon atoms in the alkyl radical; Alkanesulfonates with 12 to 18 carbon atoms in the alkane radical; α-olefin sulfonates with 12 to 18 carbon atoms in the olefin radical; α-sulfo fatty acid esters of Cχ2 b "- s cis fatty acid methyl ester; fatty alcohol sulfates with 8 to 18 carbon atoms in the fatty alcohol residue and Fatty alcohol ether sulfates with 12 to 16 carbon atoms in the fatty alcohol residue and 2 to 4 moles of ethylene oxide.
Die erfindungsgemäßen Reinigerkonzentrate enthalten derartige nichtionische und/oder anionische Tenside in einer Menge von 0,1 bis 10 Gew.-%, vorzugsweise in einer Menge von 1 bis 3 Gew.-%, je¬ weils bezogen auf die Gesamtzusammensetzung der Reinigerkonzen¬ trate.The cleaner concentrates according to the invention contain such nonionic and / or anionic surfactants in an amount of 0.1 to 10% by weight, preferably in an amount of 1 to 3% by weight, in each case based on the total composition of the cleaner concentrates.
In Abhängigkeit vom Alkoxylierungsgrad können die nichtionischen Tenside je nach Bedarf zum Reinigen, Emulgieren und Entschäumen herangezogen werden.Depending on the degree of alkoxylation, the nonionic surfactants can be used for cleaning, emulsifying and defoaming as required.
Bei verschiedenen Anforderungen an die Reinigungslösungen können auch Mischungen der nichtionischen Tenside eingesetzt werden. Gleiches gilt für Mischungen anionischer Tenside sowie für Mi¬ schungen von nichtionischen und anionischen Tensiden. In der Regel ist der Einsatz nichtionischer Tenside bevorzugt.Mixtures of the nonionic surfactants can also be used to meet various cleaning solution requirements. The same applies to mixtures of anionic surfactants and to mixtures of nonionic and anionic surfactants. In general, the use of nonionic surfactants is preferred.
Die erfindungsgemäßen Reinigerkonzentrate enthalten als wesentliche Bestandteile ferner eine Kombination aus a) Polyacrylsäure und/oder Alkalimetallpolyacrylaten und b) Glycerin und/oder Polyglycerin zur Stabilisierung der Dispersion.The essential constituents of the cleaner concentrates according to the invention also contain a combination of a) polyacrylic acid and / or alkali metal polyacrylates and b) glycerol and / or polyglycerol to stabilize the dispersion.
Erfindungsgemäß ist es bevorzugt, daß die Reinigerkonzentrate Polyacrylsäure und/oder Alkalimetallpolyacrylate in einer Menge von 0,5 bis 10 Gew.-%, insbesondere in einer Menge von 2 bis 6 Gew.-%, jeweils bezogen auf den in der Dispersion dispergierten Feststoff, enthalten.
Die Verwendung von Polyacrylsäure erweist sich gegenüber der neu¬ tralisierten Natrium-Form bei gleicher Molekularmasse vorteilhafter hinsichtlich der erreichten Dispersionsstabilität. Prinzipiell sind die einzusetzenden Polyacrylsäuren bereits aus der US-A-4 521 332 bekannt. Die Verwendung von Polyacrylsäuren wird gegenüber den Salzen bevorzugt, weil die freien Säuren im Gegensatz zu den Salzen deutlich besser in Wasser löslich sind und so in einem ersten Her¬ stellungsschritt sehr gut, auch in Kombination mit den verwendeten nichtionischen und/oder anionischen Tensiden, auf die zu dispergierenden Feststoffe aufgebracht werden können. Das besonders bevorzugte Molekulargewicht der Polyacrylsäuren liegt im Bereich von 500 bis 12 000, vorzugsweise unter 10 000; beste Ergebnisse wurden bei Verwendung einer 63 Gew.-%igen Lösung einer Polyacrylsäure mit einem Molekulargewicht von 2 100 erhalten. Hö¬ here Molekulargewichte der Polyacrylsäuren führten bei gleichen Aktivsubstanzgehalten lediglich zu erhöhten Viskositäten. Beim Einsatz von Alkal metallsalzen der Polyacrylsäure, wie beispiels¬ weise Natriumpolyacrylaten, ist - bezüglich der Einsatzmenge - dem Molekulargewicht des Natriums entsprechend Rechnung zu tragen.According to the invention, it is preferred that the cleaner concentrates polyacrylic acid and / or alkali metal polyacrylates in an amount of 0.5 to 10% by weight, in particular in an amount of 2 to 6% by weight, based in each case on the solid dispersed in the dispersion, contain. The use of polyacrylic acid proves to be more advantageous than the neutralized sodium form with the same molecular mass in terms of the dispersion stability achieved. In principle, the polyacrylic acids to be used are already known from US Pat. No. 4,521,332. The use of polyacrylic acids is preferred over the salts because, in contrast to the salts, the free acids are significantly more soluble in water and are therefore very good in a first production step, also in combination with the nonionic and / or anionic surfactants used the solids to be dispersed can be applied. The particularly preferred molecular weight of the polyacrylic acids is in the range from 500 to 12,000, preferably below 10,000; best results were obtained using a 63% by weight solution of a polyacrylic acid with a molecular weight of 2,100. Higher molecular weights of the polyacrylic acids only led to increased viscosities with the same active substance contents. When using alkali metal salts of polyacrylic acid, such as, for example, sodium polyacrylates, the molecular weight of the sodium must be taken into account in relation to the amount used.
Bestandteil der erfindungsgemäßen Stabilisator-Kombination sind ferner Glycerin und/oder Polyglycerin. Diese liegen in den er¬ findungsgemäßen Reinigerkonzentraten in einer Menge von 0,5 bis 10 Gew.-%, insbesondere in einer Menge von 1 bis 3 Gew.-%, jeweils bezogen auf die Gesamtzusammensetzung der Reinigerkonzentrate, vor. Polyglycerine im Sinne der vorliegenden Erfindung sind beispiels¬ weise bekannt aus Ullmanns Encyklopädie der technischen Chemie, 4. Auflage 1976, Band 12, Seite 374. Die Polyglycerine haben relative Molekülmassen von 166 (6 C-Atome) bis 2238 (90 C-Atome) und 4 bis 32 Hydroxylgruppen. Diese werden durch alkalikatalysierte Polykon- densation aus Glycerin unter Wasserabspaltung (Verknüpfung über Etherfunktionen) erhalten. Bei dieser Reaktion werden
Oligomerengemische erhalten, deren mittlerer Polymerisationsgrad sich beispielsweise über die OH-Zahl bestimmen läßt.Glycerol and / or polyglycerol are also part of the stabilizer combination according to the invention. These are present in the cleaner concentrates according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 3% by weight, in each case based on the total composition of the cleaner concentrates. For the purposes of the present invention, polyglycerols are known, for example, from Ullmanns Encyklopadie der industrial chemistry, 4th edition 1976, volume 12, page 374. The polyglycerols have relative molecular weights of 166 (6 carbon atoms) to 2238 (90 carbon atoms) and 4 to 32 hydroxyl groups. These are obtained by alkali-catalyzed polycondensation from glycerol with elimination of water (linkage via ether functions). In this reaction Obtain oligomer mixtures whose average degree of polymerization can be determined, for example, via the OH number.
Neben den oben genannten Wirkstoffkomponenten können die erfin¬ dungsgemäßen Reinigerkonzentrate auch noch weitere, in alkalischen Reinigungsmitteln üblicherweise verwendete Bestandteile enthalten. Als solche kommen insbesondere in Frage: zusätzliche alkalische Builderstoffe, Komplexbildner, Entschäumer und Korrosionsinhibi¬ toren. Beispielhaft für im Sinne der Erfindung besonders geeignete Verbindungen seien genannt:In addition to the active ingredient components mentioned above, the cleaner concentrates according to the invention can also contain further constituents which are usually used in alkaline cleaning agents. The following are particularly suitable as such: additional alkaline builders, complexing agents, defoamers and corrosion inhibitors. Examples of compounds which are particularly suitable in the context of the invention are:
Zusätzliche alkalische Builderstoffe: Alkanolamine, wie Mono-, Di¬ oder Triethanola in, Alkalimetallcarbonate, wie Natriumcarbonat, Alkali etallgluconate, insbesondere Natrium- oder Kaliumgluconat, sowie weitere Alkalimetallhydroxide, d.h. insbesondere Natrium¬ hydroxid. Die erfindungsgemäßen Reinigerkonzentrate enthalten diese zusätzlichen alkalischen Builderstoffe in einer Menge von 1 bis 15 Gew.-%, vorzugsweise 3 bis 10 Gew.-%, jeweils bezogen auf die Ge¬ samtzusammensetzung der Reinigerkonzentrate.Additional alkaline builder substances: alkanolamines, such as mono-, di- or triethanolamine, alkali metal carbonates, such as sodium carbonate, alkali metal gluconates, in particular sodium or potassium gluconate, and further alkali metal hydroxides, i.e. in particular sodium hydroxide. The cleaner concentrates according to the invention contain these additional alkaline builder substances in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, in each case based on the total composition of the cleaner concentrates.
Komplexbildner: Polycarbonsäuren, Phosphonsäuren, wie Hydroxyethan-l,l-diphosphonsäure (HEDP), Amino- tris(methylenphosphonsäure) (ATMP), A inopolycarbonsäuren, bei¬ spielsweise Ethylendiamintetraessigsäure (EDTA) oder Nitrilotri- essigsäure (NTA), Polyoxycarbonsäuren, z.B. Citronensäure, und die wasserlöslichen Salze derartiger Säuren, vorzugsweise die Natrium¬ salze. Die erfindungsgemäßen Reinigerkonzentrate können derartige Komplexbildner in einer Menge von 0,5 bis 5 Gew.-%, vorzugsweise 2 bis 4 Gew.-%, jeweils bezogen auf die Gesamtzusammensetzung der Reinigerkonzentrate, enthalten.Complexing agents: polycarboxylic acids, phosphonic acids, such as hydroxyethane-l, l-diphosphonic acid (HEDP), amino-tris (methylenephosphonic acid) (ATMP), aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), polyoxycarboxylic acids, e.g. Citric acid, and the water-soluble salts of such acids, preferably the sodium salts. The cleaning concentrates according to the invention can contain such complexing agents in an amount of 0.5 to 5% by weight, preferably 2 to 4% by weight, in each case based on the total composition of the cleaning concentrates.
Entschäumer: C^/ig-FettalkohoUKokosalkoholJ-polyethylenglykol- butylether, Ethylendiamin + 30E0 + 60P0; jeweils in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Gesamtzusammensetzung der Reiniger¬ konzentrate.
Korrosionsinhibitoren: (für Buntmetalle) Benztriazol, Tolyltriazol; jeweils in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Gesamtzu¬ sammensetzung der Reinigerkonzentrate.Defoamer: C ^ / ig fatty alcohol coconut alcohol J polyethylene glycol butyl ether, ethylenediamine + 30E0 + 60P0; in each case in amounts of 0.1 to 5% by weight, based on the total composition of the cleaner concentrates. Corrosion inhibitors: (for non-ferrous metals) benzotriazole, tolyltriazole; in each case in amounts of 0.1 to 5% by weight, based on the total composition of the cleaner concentrates.
Ein Zusatz derartiger Verbindungen ist im Rahmen der vorliegenden Erfindung keineswegs generell erforderlich; solche Additive können vielmehr je nach Anwendungsfall von Vorteil sein, wobei die jeweils erforderlichen Mengen auf den Bedarfsfall abzustimmen sind.The addition of such compounds is by no means generally necessary in the context of the present invention; Such additives can rather be advantageous depending on the application, the quantities required in each case being matched to the need.
Zur Herstellung der erfindungsgemäßen pumpfähigen alkalischen Rei¬ nigerkonzentrate geht man in der Regel in der folgenden Weise vor: Die Builderstoffe werden zunächst als Feststoffe mit den im Reini¬ ger verwendeten Netzmitteln, d.h. den nichtionischen und/oder an¬ ionischen Tensiden, und den Stabilisatoren, d.h. mit Polyacrylsäure und Glycerin/Polyglycerin, sowie den gegebenenfalls einzusetzenden weiteren Inhaltsstoffen vermischt. In einem zweiten Schritt wird dieses Gemisch in technischer 40 bis 50 Gew.-%iger wäßriger Na¬ tronlauge dispergiert. Es ist natürlich auch möglich, die Builderstoffe, Tenside, Stabilisatoren sowie die gegebenenfalls einzusetzenden weiteren Inhaltsstoffe einzeln in beliebiger Rei¬ henfolge in der vorgelegten wäßrigen Natronlauge zu dispergieren. Wichtig hierbei ist, daß dieses Dispergieren unter Einwirkung hoher Scher-, Schub- und Reibungskräfte erfolgt, beispielsweise durch den Einsatz sogenannter ROTOR-STATOR-Systeme. Als ROTOR-STATOR-Systeme werden handelsübliche Fabrikate, z.B. der Firma Janke & Kunkel GmbH & Co. (Ultra-Turrax), der Firma Silverson, der Firma Fryma (Zahn¬ kolloidmühle), der Firma Cavitron (Cavitron) oder der Firma Krupp (Supratron) verwendet. Die ROTOR-STATOR-Systeme können hierbei so¬ wohl als Kammer-, Loch- oder Kegelwerkzeuge ausgeführt sein. ,To produce the pumpable alkaline cleaner concentrates according to the invention, the procedure is generally as follows: The builder substances are firstly treated as solids with the wetting agents used in the cleaner, i.e. the nonionic and / or anionic surfactants, and the stabilizers, i.e. mixed with polyacrylic acid and glycerin / polyglycerin, as well as any other ingredients to be used. In a second step, this mixture is dispersed in technical 40 to 50% by weight aqueous sodium hydroxide solution. It is of course also possible to individually disperse the builders, surfactants, stabilizers and any other ingredients to be used in any order in the aqueous sodium hydroxide solution. It is important here that this dispersion takes place under the action of high shear, thrust and frictional forces, for example through the use of so-called ROTOR-STATOR systems. Commercially available brands are used as ROTOR-STATOR systems, e.g. from Janke & Kunkel GmbH & Co. (Ultra-Turrax), from Silverson, from Fryma (Zahn¬ colloid mill), from Cavitron (Cavitron) or from Krupp (Supratron). The ROTOR-STATOR systems can be designed as chamber, hole or cone tools. .
Die Herstellung der erfindungsgemäßen Reinigerkonzentrate kann durchaus bei Raumtemperatur erfolgen. Bevorzugt ist es jedoch, daß
dieses Dispergieren bei erhöhter Temperatur, d.h. bei Temperaturen bis 220 °C, erfolgt; insbesondere ist hier ein Temperaturbereich von 50 bis 60 °C bevorzugt. Selbstverständlich kann die Herstellung der Reinigerkonzentrate sowohl diskontinuierlich als auch kontinu¬ ierlich erfolgen.The cleaning concentrates according to the invention can be produced at room temperature. However, it is preferred that this dispersion takes place at elevated temperature, ie at temperatures up to 220 ° C; a temperature range of 50 to 60 ° C. is particularly preferred here. Of course, the cleaning concentrates can be produced both discontinuously and continuously.
Weiterhin ist Gegenstand der vorliegenden Erfindung die Verwendung der erfindungsgemäßen Reinigerkonzentrate bei der Reinigung von Metalloberflächen, insbesondere von Stahl, Buntmetallen, Kupfer, Aluminium und Zink vor Veredelungsprozessen wie Phosphatieren, Galvanisieren, Emaillieren und Lackieren sowie bei der Zwischen¬ reinigung vor Verarbeitungsprozessen, insbesondere vor der Glühe.The present invention furthermore relates to the use of the cleaner concentrates according to the invention in the cleaning of metal surfaces, in particular steel, non-ferrous metals, copper, aluminum and zinc before finishing processes such as phosphating, electroplating, enamelling and painting and in intermediate cleaning before processing processes, in particular before Glow.
Obwohl die erfindungsgemäßen Reinigerkonzentrate selbstverständlich auch in unverdünnter Form angewendet werden können, ist jedoch im Sinne der vorliegenden Erfindung bevorzugt, die Reinigerkonzentrate derart zu verwenden, daß man eine 1 bis 20 Gew.-% Reinigerkonzen¬ trat enthaltende wäßrige Lösung für die oben genannten Reinigungs¬ prozesse einsetzt. Dementsprechend enthalten bevorzugt verwendete Reinigungslösungen 10 bis 200 g/1 der erfindungsgemäßen Reiniger¬ konzentrate. Zur Bereitung von verdünnten Anwendungslösungen, d.h. Reinigungslösungen, werden die Reinigerkonzentrate in der Regel unter Rühren direkt in das Reinigungsbad eindosiert.Although the cleaner concentrates according to the invention can of course also be used in undiluted form, it is preferred for the purposes of the present invention to use the cleaner concentrates in such a way that an aqueous solution containing 1 to 20% by weight cleaner concentrate is used for the above-mentioned cleaning agents processes. Accordingly, cleaning solutions preferably used contain 10 to 200 g / 1 of the cleaner concentrates according to the invention. For the preparation of dilute application solutions, i.e. Cleaning solutions, the cleaning concentrates are usually dosed directly into the cleaning bath with stirring.
Der Vorteil der erfindungsgemäßen pumpfähigen, alkalischen Reini¬ gerkonzentrate besteht zum einen darin, daß diese einen hohen Wirkstoffgehalt an Builderstoffen und gleichzeitig eine außeror¬ dentliche Lagerstabilität aufweisen und zum anderen darin, daß diese eine einfache Dosierung erlauben.The advantage of the pumpable, alkaline cleaner concentrates according to the invention is, on the one hand, that they have a high active substance content of builder substances and, at the same time, an extraordinary storage stability and, on the other hand, that they allow simple dosing.
Somit können für alle Anwendungsfälle in der industriellen techni¬ schen Reinigung geeignete Produkte angeboten werden, beispielsweise
für das Spritz-, Bürst-, Tauch- und Ultraschallverfahren sowie für die elektrolytische Reinigung. Durch geeignete Kombinationen können vorgegebene Trübungspunkte eingestellt und so Hochtemperatur- oder Niedrigtemperatur-Reiniger zubereitet werden.
Suitable products can therefore be offered for all applications in industrial technical cleaning, for example for spraying, brushing, immersion and ultrasonic processes as well as for electrolytic cleaning. Using suitable combinations, predetermined cloud points can be set and high-temperature or low-temperature cleaners can be prepared.
BeispieleExamples
Die nachfolgend genannten Beispiele dienen der Erläuterung der Er¬ findung.The examples given below serve to explain the invention.
In den Beispielen und Vergleichsbeispielen wurden jeweils die nichtionischen Tenside zusammen mit der Polyacrylsäure-Lösung und dem Glycerin aufgeschmolzen und dieses Gemisch anschließend in ei¬ nem Labormischer mit den Builderstoffen, d.h. insbesondere Natriummetasilicat und/oder Natriumpyrophosphat, vermischt. Hieran anschließend wurde diese Mischung in eine im Handel erhältliche 50 Gew.-%ige Natronlauge eingerührt, auf 60 °C erwärmt und anschlie¬ ßend mit einem Hochleistungsdispergierer dispergiert. Die erfindungsgemäßen Dispersionen sind bei Raumtemperatur über mehrere Wochen absetzstabil und zeigen keine Änderung des Fließverhaltens, während bei nicht erfindungsgemäßen Dispersionen schon nach relativ kurzer Zeit eine Phasentrennung beobachtet werden konnte, die ent¬ sprechende Produkte für die technische Anwendung ungeeignet macht.In the examples and comparative examples, the nonionic surfactants were melted together with the polyacrylic acid solution and the glycerol, and this mixture was then mixed with the builder substances in a laboratory mixer. especially sodium metasilicate and / or sodium pyrophosphate, mixed. This mixture was then stirred into a commercially available 50% by weight sodium hydroxide solution, heated to 60 ° C. and then dispersed using a high-performance disperser. The dispersions according to the invention are stable to settling for several weeks at room temperature and show no change in the flow behavior, whereas with dispersions not according to the invention a phase separation could be observed after a relatively short time, making the corresponding products unsuitable for industrial use.
Beispiel 1example 1
Gemäß der obigen Arbeitsvorschrift wurde ein pumpfähiges alkali¬ sches Reinigerkonzentrat hergestellt aus 53 Gew.-% einer 50 %igen Natronlauge, 40,3 Gew.-% Natriummetasilicat K0 mit einer Teilchen¬ größenverteilung 20 % < 0,4 mm, 40 % < 0,2 mm, 20 % < 0,1 mm und 15 % < 0,05 mm (Natriummetasilicat K0 - Na2Siθ3, wasserfrei).In accordance with the above working instructions, a pumpable alkaline cleaner concentrate was produced from 53% by weight of a 50% sodium hydroxide solution, 40.3% by weight sodium metasilicate K0 with a particle size distribution of 20% <0.4 mm, 40% <0 , 2 mm, 20% <0.1 mm and 15% <0.05 mm (sodium metasilicate K0 - Na2Siθ3, anhydrous).
Das Reinigerkonzentrat enthielt weiterhin 1,7 Gew.-% Polyacrylsäure (Good-Rite K 752 (63 %)) mit einem Molekulargewicht von 2100 und einem Natriumgehalt von 0,8 % mit einem pH-Wert im Bereich von 2,2 bis 3. Als nichtionische Tensid-Basis diente eine Kombination aus gleichen Teilen eines C^-iß-Fettalkoholen mi't 14 E0 (0HZ 68 ^1S
74, AS 100 %) und eines modifizierten Fettalkoholpolyglycolethers auf der Basis von Kokoslorol mit 9,5 EO, Butylether verschlossen. Das Gemisch der beiden Tenside ist in dem Reinigungskonzentrat in einer Menge von 2 Gew.-% enthalten. Darüber hinaus enthält das Reinigungskonzentrat 3 Gew.-% Glycerin.The cleaner concentrate also contained 1.7% by weight of polyacrylic acid (Good-Rite K 752 (63%)) with a molecular weight of 2100 and a sodium content of 0.8% with a pH in the range from 2.2 to 3. Suitable nonionic surfactant-based, a combination of equal parts of a served C ^ -iß fatty alcohols mi 't 14 E0 (0HZ 68 ^ 1S 74, AS 100%) and a modified fatty alcohol polyglycol ether based on coconut chlorol with 9.5 EO, butyl ether. The mixture of the two surfactants is contained in the cleaning concentrate in an amount of 2% by weight. The cleaning concentrate also contains 3% by weight of glycerin.
Selbst nach mehreren Wochen Lagerung bei Raumtemperatur trat keine Phasentrennung auf.No phase separation occurred even after several weeks of storage at room temperature.
Beispiel 2Example 2
Unter Verwendung von 8,0 Gew.-% festem Natriumhydroxid, 74,7 Gew.-% 50 Gew.-%iger Natronlauge, 0,9 Gew.-% Diglycerin (0HZ 1300), 9,6 Gew.-% Natriumpyrophosphat (Tetranatriumdiphosphat a p2θ7), 3,2 Gew.-% Natriumgluconat, 1,1 Gew.-% der oben genannten Polyacryl¬ säure, 1,4 Gew.- des oben genannten nichtionischen Tensidgemisches und 1,1 Gew.-% Glycerin wurde ein pumpfähiges alkalisches Reini¬ gerkonzentrat hergeste11t.Using 8.0% by weight solid sodium hydroxide, 74.7% by weight 50% by weight sodium hydroxide solution, 0.9% by weight diglycerin (0HZ 1300), 9.6% by weight sodium pyrophosphate ( Tetrasodium diphosphate a p2θ7), 3.2% by weight of sodium gluconate, 1.1% by weight of the above-mentioned polyacrylic acid, 1.4% by weight of the above-mentioned nonionic surfactant mixture and 1.1% by weight of glycerol were added pumpable alkaline cleaner concentrate.
Auch nach 8 Wochen trat keine Phasentrennung auf.No phase separation occurred even after 8 weeks.
Beispiel 3Example 3
Analog Beispiel 2 jedoch unter Verwendung von 0,6 Gew.-% Polyacrylsäure, 9,7 Gew.-% Natriumpyrophosphat und 75,1 Gew.-% 50 %iger Natronlauge anstelle der in Beispiel 2 entsprechend genannten Rezepturbestandteile konnte ebenfalls ein über 8 Wochen stabiles Reinigerkonzentrat erhalten werden.Analogously to Example 2, but using 0.6% by weight of polyacrylic acid, 9.7% by weight of sodium pyrophosphate and 75.1% by weight of 50% sodium hydroxide solution instead of the formulation constituents correspondingly mentioned in Example 2, it was also possible to use for 8 weeks stable cleaner concentrate can be obtained.
Verqleichsbeispiel 1
Unter Verwendung von 54,7 Gew.-% 50 %iger Natronlauge, 41,5 Gew.-% des oben genannten Natriu metasilicats, 1,8 Gew.-% der oben ge¬ nannten Polyacrylsäure, 2,0 Gew.- der obigen Tensidbasis, jedoch ohne Verwendung von Glycerin, wurde ein Reinigerkonzentrat herge¬ stellt. Bereits nach 2 Tagen trat eine Phasentrennung auf.Comparative Example 1 Using 54.7% by weight of 50% sodium hydroxide solution, 41.5% by weight of the above-mentioned sodium metasilicate, 1.8% by weight of the above-mentioned polyacrylic acid, 2.0% by weight of the above A cleaner concentrate was prepared based on the surfactant, but without the use of glycerol. A phase separation occurred after only 2 days.
Verqleichsbeispiel 2Comparative Example 2
Unter Verwendung von 53,9 Gew.-% der 50 %igen Natronlauge, 41,0 Gew.-% des oben genannten Natriummetasilicats, 2 Gew.-% der obigen Tensidbasis und 3,1 Gew.-% Glycerin wurde ein Reinigerkonzentrat hergestellt, bei dem jedoch nach einem Tag bereits eine Phasen¬ trennung auftrat.A cleaner concentrate was prepared using 53.9% by weight of the 50% sodium hydroxide solution, 41.0% by weight of the above sodium metasilicate, 2% by weight of the above surfactant base and 3.1% by weight of glycerin. in which, however, a phase separation already occurred after one day.
Verqieichsbeispiel 3Comparative Example 3
Unter Verwendung von 8,2 Gew.-% Natriumhydroxid (fest), 76,2 Gew.-% 50 %iger Natronlauge, 9,8 Gew.-% des Natriumpyrophosphats, 3,3 Gew.-% Natriumgluconat, 1,1 Gew.- Polyacrylsäure und 1,4 Gew.-% der oben genannten Tensidbasis wurde ein Reinigerkonzentrat her¬ gestellt, bei dem jedoch nach 3 Tagen bereits eine Phasentrennung auftrat.Using 8.2% by weight of sodium hydroxide (solid), 76.2% by weight of 50% sodium hydroxide solution, 9.8% by weight of the sodium pyrophosphate, 3.3% by weight of sodium gluconate, 1.1% by weight .- Polyacrylic acid and 1.4 wt .-% of the above-mentioned surfactant base, a cleaner concentrate was produced, in which, however, a phase separation occurred after 3 days.
Verqleichsbeispiel 4Comparative Example 4
Unter. Verwendung von 8,2 Gew.-% Natriumhydroxid (fest), 75,4 Gew.-% 50 %iger Natronlauge, 0,9 Gew.-% Diglycerin, 9,8 Gew.-% Natrium¬ pyrophosphat, 3,2 Gew.-% Natriumgluconat, 1,4 Gew.-% Tensidbasis und 1,1 Gew.-% Glycerin wurde ein Reinigerkonzentrat hergestellt, bei dem jedoch nach" einem Tag bereits eine Phasentrennung auftrat.
Under. Use of 8.2% by weight sodium hydroxide (solid), 75.4% by weight 50% sodium hydroxide solution, 0.9% by weight diglycerin, 9.8% by weight sodium pyrophosphate, 3.2% by weight .-% sodium gluconate, 1.4 wt .-% surfactant and 1.1 wt .-% glycerol, a cleaner concentrate was produced, in which, however, a phase separation already occurred after " one day.
Claims
1. Lagerstabile, pumpfähige, alkalische Reinigerkonzentrate, be¬ stehend aus wäßrigen Dispersionen auf Basis von Alkalimetall¬ hydroxiden, die Alkalimetallsilicate und/oder Alkalimetallphosphate als alkalische Builderstoffe sowie nichtionische und/oder anio¬ nische Tenside und gegebenenfalls weitere Builderstoffe und/oder Komplexbildner und/oder weitere an sich bekannte Wirk- oder Hilfs¬ stoffe dispergiert enthalten, dadurch gekennzeichnet, daß sie als Stabilisatoren eine Kombination aus a) Polyacrylsäure und/oder Alkalimetallpolyacrylaten und b) Glycerin und/oder Polyglycerin aufweisen.1. Storage-stable, pumpable, alkaline cleaner concentrates, consisting of aqueous dispersions based on alkali metal hydroxides, the alkali metal silicates and / or alkali metal phosphates as alkaline builder substances and nonionic and / or anionic surfactants and optionally other builder substances and / or complexing agents and / / or further dispersed active or auxiliary substances known per se, characterized in that they have a combination of a) polyacrylic acid and / or alkali metal polyacrylates and b) glycerol and / or polyglycerol as stabilizers.
2. Reinigerkonzeπtrate nach Anspruch 1, dadurch gekennzeichnet, daß sie als Alkalimetall Natrium und/oder Kalium, insbesondere Na¬ trium, enthalten.2. Reinigerkonzeπtrate according to claim 1, characterized in that they contain sodium and / or potassium, in particular sodium as alkali metal.
3. Reinigerkonzentrate nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß sie als Alkalimetallhydroxid eine 40 bis 50 Gew.-%ige wäßrige Lösung von Natriumhydroxid enthalten.3. cleaner concentrates according to claim 1 or 2, characterized gekenn¬ characterized in that they contain a 40 to 50 wt .-% aqueous solution of sodium hydroxide as alkali metal hydroxide.
4. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie als Alkalimetallsilicate Natriums licate mit einem Molverhältnis Siθ2/Na2θ im Bereich von 1:1 bis 3,5:1, vorzugsweise 1:1, enthalten.4. cleaner concentrates according to one or more of claims 1 to 3, characterized in that they contain as alkali metal silicates sodium licate with a molar ratio SiO 2 / Na 2 O in the range of 1: 1 to 3.5: 1, preferably 1: 1.
5. Reinigerkonzentrate nach Anspruch 4, dadurch gekennzeichnet, daß sie Natriumsilicate in einer Menge von 5 bis 80 Gew.-%, bezogen auf die wäßrige Natriumhydroxid-Lösung, enthalten, wobei das resultierende Molverhältnis Siθ /Na2θ, bezogen auf Natriumsilicat und Natriumhydroxid, vorzugsweise im Bereich von 0,1:1 bis 0,5:1 liegt.5. cleaner concentrates according to claim 4, characterized in that they contain sodium silicates in an amount of 5 to 80 wt .-%, based on the aqueous sodium hydroxide solution, the resulting molar ratio Siθ / Na2θ, based on sodium silicate and sodium hydroxide, is preferably in the range from 0.1: 1 to 0.5: 1.
6. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie als Alkalimetallphosphate Natriumtriphosphat und/oder Natriumpyrophosphat, vorzugsweise Natriumpyrophosphat, enthalten.6. cleaner concentrates according to one or more of claims 1 to 3, characterized in that they contain sodium triphosphate and / or sodium pyrophosphate, preferably sodium pyrophosphate, as alkali metal phosphates.
7. Reinigerkonzentrate nach Anspruch 6, dadurch gekennzeichnet, daß sie die Natriumphosphate in einer Menge von 5 bis 50 Gew.-%, vorzugsweise 10 bis 50 Gew.-%, jeweils bezogen auf die wäßrige Natriumhydroxid-Lösung, enthalten.7. cleaner concentrates according to claim 6, characterized in that they contain the sodium phosphates in an amount of 5 to 50 wt .-%, preferably 10 to 50 wt .-%, each based on the aqueous sodium hydroxide solution.
8. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die nichtionischen Tenside aus¬ gewählt sind aus der Gruppe der Anlagerungsprodukte von jeweils 1 bis 14 Mol Ethylenoxid oder Propylenoxid an Fettalkohole mit 12 bis 18 C-Atomen, Oxoalkohole mit 9 bis 15 C-Atomen, Fetta ine mit 12 bis 18 C-Atomen und Nonylphenol oder deren Gemischen.8. cleaner concentrates according to one or more of claims 1 to 7, characterized in that the nonionic surfactants are selected aus¬ from the group of adducts of 1 to 14 moles of ethylene oxide or propylene oxide with fatty alcohols having 12 to 18 carbon atoms, oxo alcohols with 9 to 15 carbon atoms, fatty acids with 12 to 18 carbon atoms and nonylphenol or mixtures thereof.
9. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die anionischen Tenside ausge¬ wählt sind aus: geradkettigen oder verzweigten, gesättigten oder ungesättigten Carbonsäuren mit 10 bis 18 C-Atomen und deren Alka- limetallsalzen, Alkylbenzolsulfonaten mit 8 bis 18 C-Atomen im Alkylrest, Alkansulfonaten mit 12 bis 18 C-Atomen im Alkanrest, α-Olefinsulfonaten mit 12 bis 18 C-Atomen im Olefinrest, α- Sulfofettsäureestern von C 2 bi*5 Ci8-Fettsäuremethylestern, Fett¬ alkoholsulfaten mit 8 bis 18 C-Atomen im Fettalkoholrest und Fettalkoholethersulfaten mit 12 bis 16 C-Atomen im Fettalkoholrest und 2 bis 4 Mol Ethylenoxid oder deren Gemischen. 9. cleaner concentrates according to one or more of claims 1 to 7, characterized in that the anionic surfactants are selected from: straight-chain or branched, saturated or unsaturated carboxylic acids having 10 to 18 carbon atoms and their alkali metal salts, alkylbenzenesulfonates having 8 up to 18 carbon atoms in the alkyl radical, alkane sulfonates with 12 to 18 carbon atoms in the alkane radical, α-olefin sulfonates with 12 to 18 carbon atoms in the olefin radical, α-sulfofatty acid esters of C 2 bi * 5 Ci8 fatty acid methyl esters, fatty alcohol sulfates with 8 up to 18 carbon atoms in the fatty alcohol residue and fatty alcohol ether sulfates with 12 to 16 carbon atoms in the fatty alcohol residue and 2 to 4 moles of ethylene oxide or mixtures thereof.
10. Reinigerkonzentrate nach Anspruch 8 oder 9, dadurch gekenn¬ zeichnet, daß sie nichtionische und/oder anionische Tenside in ei¬ ner Menge von 0,1 bis 10 Gew.-%, vorzugsweise 1 bis 3 Gew.-%, je¬ weils bezogen auf die Gesamtzusammensetzung der Reinigerkonzen¬ trate, enthalten.10. cleaner concentrates according to claim 8 or 9, characterized gekenn¬ characterized in that they non-ionic and / or anionic surfactants in a quantity of 0.1 to 10 wt .-%, preferably 1 to 3 wt .-%, respectively based on the total composition of the cleaner concentrates.
11. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß sie Polyacrylsäure und/oder Alkal metallpolyacrylate, vorzugsweise Polyacrylsäure, in einer Menge von 0,5 bis 10 Gew.-%, vorzugsweise 2 bis 6 Gew.-%, jeweils bezogen auf den in der Dispersion dispergierten Feststoff, enthal¬ ten.11. cleaner concentrates according to one or more of claims 1 to 10, characterized in that they polyacrylic acid and / or alkali metal polyacrylates, preferably polyacrylic acid, in an amount of 0.5 to 10 wt .-%, preferably 2 to 6 wt .-% , each based on the solid dispersed in the dispersion.
12. Reinigerkonzentrate nach Anspruch 11, dadurch gekennzeichnet, daß das Molekulargewicht"der Polyacrylsäuren im Bereich von 500 bis 12000 liegt.12. cleaner concentrates according to claim 11, characterized in that the molecular weight "of the polyacrylic acids is in the range of 500 to 12000.
13. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß sie Glycerin und/oder Polygly- cerin in einer Menge von 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 3 Gew.-%, jeweils bezogen auf die Gesamtzusammensetzung der Reini- gerkoτizenträte, enthalten.13. cleaner concentrates according to one or more of claims 1 to 10, characterized in that they each contain glycerol and / or polyglycerol in an amount of 0.5 to 10 wt .-%, preferably 1 to 3 wt .-% on the total composition of the cleaner co-centers.
14. Reinigerkonzentrate nach Anspruch 13, dadurch gekennzeichnet, daß die Polyglycerine relative Molekulargewichte im Bereich von 166 bis 2238 und 4 bis 32 Hydroxylgruppen aufweisen.14. cleaner concentrates according to claim 13, characterized in that the polyglycerols have relative molecular weights in the range from 166 to 2238 and 4 to 32 hydroxyl groups.
15. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß sie zusätzliche alkalische Bu lderstoffe, vorzugsweise ausgewählt aus Alkanolaminen, Alkali¬ metallcarbonaten, Alkalimetallgluconaten und weiteren Alkalimetallhydroxiden, in einer Menge von 1 bis 15 Gew.-%, vorzugsweise 3 bis 10 Gew.-%, jeweils bezogen auf die Gesamtzusam¬ mensetzung der Reinigerkonzentrate, enthalten.15. cleaner concentrates according to one or more of claims 1 to 14, characterized in that they contain additional alkaline Bu lderstoffe, preferably selected from alkanolamines, alkali metal carbonates, alkali metal gluconates and other alkali metal hydroxides, in an amount of 1 to 15 wt .-%, preferably 3 to 10 wt .-%, each based on the total composition of the cleaner concentrates.
16. Reinigerkonzentrate nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß sie Komplexbildner, vorzugs¬ weise ausgewählt aus Polycarbonsäuren, Polyoxycarbonsäuren, Amino- polycarbonsäuren, Phosphonsäuren und den wasserlöslichen Salzen derartiger Säuren, in einer Menge von 0,5 bis 5 Gew.-%, vorzugs¬ weise 2 bis 4 Gew.-%, jeweils bezogen auf die Gesamtzusammensetzung der Reinigerkonzentrate, enthalten.16. cleaner concentrates according to one or more of claims 1 to 14, characterized in that they are complexing agents, preferably selected from polycarboxylic acids, polyoxycarboxylic acids, amino-polycarboxylic acids, phosphonic acids and the water-soluble salts of such acids, in an amount of 0.5 to 5 % By weight, preferably 2 to 4% by weight, based in each case on the total composition of the cleaner concentrates.
17. Verfahren zur Herstellung von Reinigerkonzentraten nach einem oder mehreren der Ansprüche 1 bis 16, dadurch gekennzeichnet, daß man die alkalischen Builderstoffe, die nichtionischen und/oder an¬ ionischen Tenside, die Stabilisatoren sowie die gegebenenfalls einzusetzenden weiteren Inhaltsstoffe entweder einzeln in belie¬ biger Reihenfolge oder zusammen als Gemisch in der wäßrigen Lösung der Alkalimetallhydroxide, vorzugsweise unter Einwirkung hoher Scher-, Schub- und Reibungskräfte, dispergiert.17. A process for the preparation of cleaner concentrates according to one or more of claims 1 to 16, characterized in that the alkaline builder substances, the nonionic and / or anionic surfactants, the stabilizers and any further ingredients to be used either individually in any amount Order or together as a mixture in the aqueous solution of the alkali metal hydroxides, preferably under the action of high shear, shear and friction, dispersed.
18. Verwendung von Reinigerkonzentraten nach einem oder mehreren der Ansprüche 1 bis 16 zur Reinigung von Metalloberflächen, insbe¬ sondere von Stahl, Buntmetallen, Kupfer, Aluminium und Zink, vor Prozessen zur Veredelung derselben, vorzugsweise vor dem Phospha¬ tieren, Galvanisieren, Emaillieren und Lackieren, sowie bei der Zwischenreinigung derselben vor Verarbeitungsprozessen, insbeson¬ dere vor der Glühe.18. Use of cleaner concentrates according to one or more of claims 1 to 16 for cleaning metal surfaces, in particular steel, non-ferrous metals, copper, aluminum and zinc, before processes for finishing them, preferably before phosphating, electroplating, enamelling and Painting, as well as in the intermediate cleaning of the same before processing, in particular before the annealing.
19. Verwendung nach Anspruch 18, dadurch gekennzeichnet, daß man die Reinigerkonzentrate in Form einer 1 bis 20 Gew.-%igen wäßrigen Lösung einsetzt. 19. Use according to claim 18, characterized in that the cleaner concentrates are used in the form of a 1 to 20% by weight aqueous solution.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4216405 | 1992-05-18 | ||
| DE4216405A DE4216405A1 (en) | 1992-05-18 | 1992-05-18 | Pumpable alkaline cleaner concentrates |
| PCT/EP1993/001147 WO1993023522A1 (en) | 1992-05-18 | 1993-05-11 | Pumpable alkaline cleaning concentrates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0642575A1 true EP0642575A1 (en) | 1995-03-15 |
| EP0642575B1 EP0642575B1 (en) | 1997-04-09 |
Family
ID=6459163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93909939A Expired - Lifetime EP0642575B1 (en) | 1992-05-18 | 1993-05-11 | Pumpable alkaline cleaning concentrates |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5520841A (en) |
| EP (1) | EP0642575B1 (en) |
| JP (1) | JPH07506608A (en) |
| KR (1) | KR950701680A (en) |
| AT (1) | ATE151457T1 (en) |
| AU (1) | AU660546B2 (en) |
| CA (1) | CA2136172A1 (en) |
| DE (2) | DE4216405A1 (en) |
| ES (1) | ES2100533T3 (en) |
| WO (1) | WO1993023522A1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4361605B2 (en) * | 1995-11-17 | 2009-11-11 | ジョンソンディバーシー・インコーポレーテッド | Cleaning formulations, cleaning formulation additives and methods for cleaning bottles using such formulations |
| CA2190235A1 (en) * | 1995-11-20 | 1997-05-21 | Barry Weinstein | High alkali-containing cleaning concentrates |
| FR2744132B1 (en) * | 1996-01-31 | 1998-04-24 | Rhone Poulenc Chimie | BASIC SYSTEM OF A NON-IONIC SURFACTANT AND AN ALKALINE METAL SILICATE, IN THE FORM OF A DISPERSION OR PELLETS AND ITS USE IN DETERGENCE |
| DE19741874A1 (en) * | 1997-09-23 | 1999-04-01 | Henkel Ecolab Gmbh & Co Ohg | Alcoholic cleaner |
| AU1295999A (en) * | 1997-11-04 | 1999-05-24 | Henkel Corporation | Process for avoiding foaming during cleaning of metal salts of intermediate length carboxylic acids from surfaces |
| WO1999024534A1 (en) * | 1997-11-06 | 1999-05-20 | Henkel Corporation | Cleaning metal salts of intermediate length carboxylic acids from surfaces |
| JP3262523B2 (en) | 1997-12-18 | 2002-03-04 | 宇野醤油株式会社 | Transparent liquid detergent containing sodium silicate |
| WO1999031209A1 (en) | 1997-12-18 | 1999-06-24 | Uno Shoyu Co., Ltd. | Transparent liquid detergent containing alkylbenzenesulfonate anionic surfactant and sodium silicate |
| US6194371B1 (en) | 1998-05-01 | 2001-02-27 | Ecolab Inc. | Stable alkaline emulsion cleaners |
| WO2000008124A1 (en) * | 1998-08-07 | 2000-02-17 | Unilever N.V. | Highly alkaline warewashing detergent and method of manufacture thereof |
| JP2001021687A (en) * | 1999-07-02 | 2001-01-26 | Ebara Kogyo Senjo Kk | Method for treating radioactive contaminant and device used for this method |
| US6727214B1 (en) | 1999-10-14 | 2004-04-27 | Henkel Corporation | Cleaning metal salts of intermediate length carboxylic acids from surfaces |
| DE10002710A1 (en) * | 2000-01-22 | 2001-08-02 | Henkel Ecolab Gmbh & Co Ohg | Production of creamy alkaline-aqueous cleaning agents containing complexing agents |
| KR100420980B1 (en) * | 2000-12-16 | 2004-03-02 | (주)아이티엠 코퍼레이션 건축사사무소 | Surface cleaner of aluminium ware of buildings and the method of construction |
| US6818604B2 (en) * | 2001-10-04 | 2004-11-16 | Speedfam-Ipec Corporation | System and method for cleaning workpieces |
| ITBS20030015A1 (en) * | 2003-02-20 | 2004-08-21 | Bettari Detergenti S R L | METHOD FOR THE PREPARATION OF A CLEANING AGGLOMERATE OF SOLID APPEARANCE AND RESULTING PRODUCT. |
| US20040180806A1 (en) * | 2003-03-06 | 2004-09-16 | Hilbert Esselbrugge | Stabilized foam control compositions, their preparation, and use |
| DE102005050556B8 (en) * | 2005-10-17 | 2007-07-26 | Mack Gmbh | Process for cleaning metal-containing surfaces and use of a cleaning solution |
| DE102005055768A1 (en) * | 2005-11-21 | 2007-05-24 | Ralf Waldmann | Method and means for the electrolytic cleaning and descaling of a metallic workpiece |
| ES2385469T3 (en) * | 2006-06-06 | 2012-07-25 | Hydro Aluminium Rolled Products Gmbh | Surface conditioning method of a lithographic sheet or lithographic strip |
| CN101265583A (en) * | 2007-03-16 | 2008-09-17 | 深圳富泰宏精密工业有限公司 | Cleaning medicine and method for cleaning metallic surface using same |
| US20120115766A1 (en) * | 2009-06-01 | 2012-05-10 | Yuken Industry Co., Ltd. | Degreasing composition and production method thereof |
| BR102012010852A2 (en) * | 2012-05-08 | 2015-04-14 | Oxiprana Ind Quimica Ltda | LEAD-FREE GALVANIZATION PROCESS FOR METAL MATERIALS |
| WO2014107578A1 (en) * | 2013-01-03 | 2014-07-10 | Basf Corporation | Homogeneous detergent composition |
| PL2806002T3 (en) * | 2013-05-24 | 2019-03-29 | Macdermid Enthone Inc. | Aqueous stripping composition for the removal of polymeric surface sealants on metal surfaces |
| JP6533030B2 (en) * | 2013-12-17 | 2019-06-19 | 第一工業製薬株式会社 | Cleaning composition for silicon wafer |
| ZA201508375B (en) * | 2014-11-12 | 2017-02-22 | Orangeimpact (Pty) Ltd | A method and apparatus for removing an outer layer from an elongate body of metal |
| JP6430232B2 (en) * | 2014-12-18 | 2018-11-28 | 花王株式会社 | Method for producing alkaline detergent composition for steel sheet |
| PT3156475T (en) | 2015-10-16 | 2018-10-19 | Georg Hagleitner Hans | Liquid cleaning concentrate |
| JP7279019B2 (en) * | 2017-08-31 | 2023-05-22 | ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Improved method for nickel-free phosphating of metal surfaces |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA666119A (en) * | 1960-02-02 | 1963-07-02 | A. Wright William | Liquid detergent composition |
| US3691107A (en) * | 1970-08-28 | 1972-09-12 | Stauffer Chemical Co | Novel detergent compositions |
| GB1370377A (en) * | 1971-11-15 | 1974-10-16 | Procter & Gamble Ltd | Composition and method for cleaning hard surfaces |
| US3829387A (en) * | 1972-06-22 | 1974-08-13 | American Home Prod | Caustic cleaner composition |
| US4157921A (en) * | 1978-02-13 | 1979-06-12 | American Home Products Corporation | Oven cleaning method and composition |
| US4521332A (en) * | 1981-03-23 | 1985-06-04 | Pennwalt Corporation | Highly alkaline cleaning dispersion |
| US4396525A (en) * | 1981-09-14 | 1983-08-02 | Lever Brothers Company | Phosphate free liquid scouring composition |
| DE3246080A1 (en) * | 1982-12-13 | 1984-06-14 | Henkel KGaA, 4000 Düsseldorf | CLEANING PROCEDURE |
| GB8307036D0 (en) * | 1983-03-15 | 1983-04-20 | Interox Chemicals Ltd | Peroxygen compounds |
| US4601845A (en) * | 1985-04-02 | 1986-07-22 | Lever Brothers Company | Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials |
| DE3601798A1 (en) * | 1985-04-18 | 1986-10-23 | Henkel KGaA, 40589 Düsseldorf | MULTIPURPOSE CLEANER FOR HARD SURFACES |
| US4784788A (en) * | 1985-12-14 | 1988-11-15 | Colgate-Palmolive Co. | Cleaning paste with soluble abrasive |
| CA1323280C (en) * | 1987-07-31 | 1993-10-19 | Mario Bulfari | Liquid detergent compositions |
-
1992
- 1992-05-18 DE DE4216405A patent/DE4216405A1/en not_active Withdrawn
-
1993
- 1993-05-11 AT AT93909939T patent/ATE151457T1/en not_active IP Right Cessation
- 1993-05-11 ES ES93909939T patent/ES2100533T3/en not_active Expired - Lifetime
- 1993-05-11 WO PCT/EP1993/001147 patent/WO1993023522A1/en not_active Ceased
- 1993-05-11 JP JP5519857A patent/JPH07506608A/en active Pending
- 1993-05-11 AU AU40663/93A patent/AU660546B2/en not_active Ceased
- 1993-05-11 EP EP93909939A patent/EP0642575B1/en not_active Expired - Lifetime
- 1993-05-11 CA CA002136172A patent/CA2136172A1/en not_active Abandoned
- 1993-05-11 DE DE59306127T patent/DE59306127D1/en not_active Expired - Fee Related
- 1993-05-11 KR KR1019940704142A patent/KR950701680A/en not_active Abandoned
-
1995
- 1995-01-18 US US08/338,486 patent/US5520841A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9323522A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR950701680A (en) | 1995-04-28 |
| EP0642575B1 (en) | 1997-04-09 |
| AU660546B2 (en) | 1995-06-29 |
| JPH07506608A (en) | 1995-07-20 |
| DE59306127D1 (en) | 1997-05-15 |
| ATE151457T1 (en) | 1997-04-15 |
| ES2100533T3 (en) | 1997-06-16 |
| WO1993023522A1 (en) | 1993-11-25 |
| DE4216405A1 (en) | 1993-11-25 |
| AU4066393A (en) | 1993-12-13 |
| US5520841A (en) | 1996-05-28 |
| CA2136172A1 (en) | 1993-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0642575B1 (en) | Pumpable alkaline cleaning concentrates | |
| DE3708330A1 (en) | LIQUID, ALKALINE CLEANER CONCENTRATES | |
| EP0116171B1 (en) | A caustic based aqueous cleaning composition | |
| DE68924189T2 (en) | A liquid cleaning composition containing a non-polar solvent. | |
| DE3851096T2 (en) | Process for the preparation of an aqueous liquid detergent composition containing perborate bleach. | |
| EP0710274B1 (en) | High wetting-power detergent | |
| EP0282921A1 (en) | Liquid, phosphate-free, one phase degreasing agent for aluminium surfaces | |
| EP0511253B1 (en) | Anti-froth cleaning agents and use thereof | |
| EP0506751B1 (en) | Use of a combination of non-ionic surface-active agents | |
| DE1243313B (en) | Liquid detergent concentrate | |
| DE2257642A1 (en) | BIODEGRADABLE DETERGENTS AND DETERGENTS | |
| DE3246080A1 (en) | CLEANING PROCEDURE | |
| EP0336263A2 (en) | Process for the preparation of fatty alcohol polyglycol ethers with reduced residual EO or PO content | |
| DE2125965C3 (en) | Detergents, in particular for metal, glass and fireproof materials | |
| EP0132792A1 (en) | Water soluble powdery cleaning agent for hard surfaces | |
| EP0243907A2 (en) | Use of alkylaminopolyglycol ethers as foam-suppressing additives in low-foaming detergents | |
| EP0755428B1 (en) | Use of aliphatic amine ethoxylates in aqueous cleaning agents for hard surfaces | |
| EP0605495B1 (en) | Fatty-alcohol polyalkylene glycols with a narrow homologous-series distribution in low-foam dip-cleaning agents | |
| DE3905671C2 (en) | Detergent granules suitable for the production of aqueous concentrates | |
| DE4041172A1 (en) | LIQUID SOAP PREPARATION | |
| DE19828578A1 (en) | Production of alkaline-aqueous cleaning creams useful for cleaning hard surface and textiles | |
| EP0658187B1 (en) | Alkaline liquid cleaning agents containing di-salts of sulphooleic acids, and the use of such agents | |
| AT278216B (en) | WETTING, DETERGENT, CLEANING AGENTS AND DETERGENTS | |
| CH637690A5 (en) | AQUEOUS DETERGENT SOLUTIONS. | |
| EP4636064A1 (en) | Use of alkoxylated fatty alcohols for improving the low-temperature cleaning of metallic components |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19941109 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES FR NL |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| 17Q | First examination report despatched |
Effective date: 19960514 |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE ES FR NL |
|
| REF | Corresponds to: |
Ref document number: 151457 Country of ref document: AT Date of ref document: 19970415 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 59306127 Country of ref document: DE Date of ref document: 19970515 |
|
| ET | Fr: translation filed | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2100533 Country of ref document: ES Kind code of ref document: T3 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19990512 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000508 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20000510 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000511 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20000531 Year of fee payment: 8 Ref country code: ES Payment date: 20000531 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000717 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010512 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010531 |
|
| BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 20010531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011201 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020131 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20011201 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020301 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030303 |